Addition of hydrogen halides to the alkenes

Markovnivov addition (halogen atom always adds to most substituted carbon

You get a carbocation

Recall that tertiary > secondary > primary > methyl in terms of carbocation stability.

The more highly substituted carbocation will be formed and subsequently attacked by halide anion

- Results in the halogen atom adding to the most highly substituted carbon atom of the
alkene

Regioselectiive reaction reacts preferentially at some site, favours formation of one isomer over
another

Note that when HBr is added to 2-methylpropene, 1-bromo-2-methylpropane is not observed

(formation of an unstable primary carbocation)

Carbocations (sp2 hybridized carbons and therefore planar in nature)

The empty 2p orbital is perpendicular to the plane of the molecule

If the carbocation is located on a carbon with branches, or alkyl substituents, there is overlap between
the empty 2p orbital of the carbocation and the adjacent sigma bond

- This is a process known as hyperconjugation

The more branching present, the more hyperconjugation is possible, and as a result the stability of the
carbocation increases; the formal charge on the carbon possessing the carbocation is slightly diminished
(recall Zeliskos Rule of Happy Molecules?)
You can occupy the p orbital transiently with electrons

In some cases, the carbocation that is initially formed during an addition reaction is not necessarily the
most stable carbocation that the molecule can accommodate

In these special instances the moleculein question can undergo a skeletal rearrangements to form the
most stable carbocation

Lower line = more stable (tert butyl

There is no advantage to a rearrangement